EP0560326B1 - Compositions de copolymères statistiques de propène et comonomères d'alpha-olefines - Google Patents

Compositions de copolymères statistiques de propène et comonomères d'alpha-olefines Download PDF

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Publication number
EP0560326B1
EP0560326B1 EP93103846A EP93103846A EP0560326B1 EP 0560326 B1 EP0560326 B1 EP 0560326B1 EP 93103846 A EP93103846 A EP 93103846A EP 93103846 A EP93103846 A EP 93103846A EP 0560326 B1 EP0560326 B1 EP 0560326B1
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Prior art keywords
fraction
olefin
composition
weight
percent
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Expired - Lifetime
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EP93103846A
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German (de)
English (en)
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EP0560326A1 (fr
Inventor
Giuliano Cecchin
Floriano Guglielmi
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Basell North America Inc
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Montell North America Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst

Definitions

  • the present invention relates to a composition of random copolymers of propene comprising one or more C 4 -C 10 ⁇ -olefins as comonomer, and to a process to obtain said composition.
  • the copolymer composition according to the present invention is suitable for the production of heat-sealable film that can be used as such thanks to their mechanical and physical properties, or in the preparation of multilayer films obtained, for example, by way of coextrusion with polypropylene. Moreover, said composition can also be used in the food industry because of their low content of component soluble in xylene at room temperature.
  • compositions of copolymers of propene with an olefin mainly ethylene and/or 1-butene, or their blends with other olefin polymers, for the preparation of heat-sealable materials is known in the art.
  • US-A-4,481,336 describes compositions made up of two propene/ethylene and/or butene copolymer fractions, said compositions having heat-sealable, clarity, and nonsticking properties.
  • Said patent teaches that the butene content in the copolymeric fraction present in lower quantities must be greater than 25% by weight with respect to the total monomers, and the quantity of propene must be less than 75% by weight. If said quantities are not adhered to as regards respectively the lower and upper limits, the composition obtained would have poor heat sealability.
  • the film obtained by using said compositions should not be oriented, otherwise the portion of the film subjected to sealing could shrink during the heat-sealing process.
  • US-A-4,822,840 describes copolymer compositions comprising propene/ethylene/ ⁇ -olefins random copolymers.
  • the propene is the principal component, and the ethylene is present in quantities ranging from 0.2 to 3.5% by weight.
  • EP-A-0 483 523 concerns a composition comprising a copolymer of propene with an ⁇ -olefin, and, preferably, an ethylene/propene copolymer as the second copolymer.
  • EP-A-0 263 718 discloses a low-crystalline propylene polymer composition having improved heat sealability and suitable for producing films and composite laminated structures, e.g. for use in food packaging.
  • Said composition is prepared by a sequential polymerization process carried out in two stages and comprises:
  • compositions known up to now have characteristics which are not adequate for some of the uses for which said compositions are destined.
  • the disadvantages of said compositions are due to a heat-seal temperature which is not sufficiently low, a solubility in xylene at 25°C which is too high, and a low crystallinity.
  • compositions with a low heat-sealing temperature they must also have a low melting point.
  • a new composition has now been found having low solubility in xylene and lower heat-sealing temperature, but a high melting point.
  • a particular advantage of the copolymer composition of the present invention is that it is particularly useful for the production of laminated mono- or bioriented films having a low heat-sealing temperature.
  • a further advantage of the copolymer compositions of the present invention is their rigidity. Said compositions are much more rigid compared to the compositions known in the art.
  • Object of the present invention is a semicrystalline polyolefin composition comprising (by weight):
  • the preferred C 4 -C 10 ⁇ -olefins are 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Particularly preferred is 1-butene.
  • the C 4 -C 10 ⁇ -olefins of Fractions A and B are the same.
  • the preferred percent of C 4 -C 10 ⁇ -olefins in Fraction A is from 3 to 8% by weight, while in Fraction B the preferred percent is from 20 to 30% by weight.
  • composition of the invention are as follows: melting point: from 135° to 150°C; fraction soluble in xylene at 25°C: less than 16%; flexural modulus: higher than 700 MPa; heat sealing temperature: from 90° to 105°C.
  • composition of the invention is preferably prepared by way of sequential polymerization of the monomers in the presence of Ziegler-Natta stereospecific catalysts ,supported on magnesium dihalides in active form.
  • Said catalysts contain, as an essential element, a solid catalyst component comprising a titanium compound having at least one titanium-halogen bond, and an electron-donor compound, both supported on magnesium dihalides in active form.
  • the magnesium dihalide support is present preferably in the form of spheroidal particles having a narrow particle size distribution.
  • the catalysts used in the process of the invention are characterized by the fact that they are capable of producing polypropylene having an isotactic index higher than 90, preferably higher than 95.
  • Catalysts which have the above mentioned characteristics are well known in patent literature. Particularly useful are the catalysts described in US-A-4,339,054, and EP-B-0 045 977. Other examples of suitable catalysts are described in US-A-4,472,524 and US-A-4,473,660.
  • the solid catalyst components used in the preparation of said catalysts contain, as electron-donor, compounds selected from ethers, ketones, lactones, compounds containing N, P, and/or S atoms, and esters of mono- and dicarboxylic acids.
  • esters of phthalic acid such as diisobutyl, dioctyl, and diphenyl phthalate, and monobutyl monobenzyl phthalate
  • malonic acid such as diisobutyl and diethyl malonate
  • the aryl and alkyl pivalates the alkyl, cycloalkyl and aryl maleates
  • the alkyl and aryl, carbonates such as diisobutyl carbonate, monoethyl monophenyl carbonate, and diphenyl carbonate
  • succinic acid such as mono- and diethyl succinate.
  • R I and R II are the same or different, and are C 1 -C 18 alkyl, C 3 -C 18 cycloalkyl, or C 6 -C 18 aryl radicals;
  • R III and R IV are the same or different, and are alkyl radicals having from 1 to 4 carbon atoms.
  • Examples representative of the ethers of formula (I) are 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, and 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane.
  • the catalyst components illustrated are prepared according to various methods. One of them consists of milling or co-milling the magnesium dihalide (anhydrous, containing less than 1% of water) with the titanium compound and the electron-donor compound, under conditions which cause the activation of the magnesium dihalide; thereafter, the milled product is treated one or more times with an excess of TiCl 4 at a temperature ranging from 80° to 135°C, and then washed repeatedly with a hydrocarbon (hexane, for example) until no more chlorine ions can be found in the wash water.
  • a hydrocarbon hexane, for example
  • the anhydrous magnesium dihalide is first preactivated using known methods, then it is reacted with an excess of TiCl 4 containing the electron-donor compound in solution.
  • the operation takes place at a temperature ranging from 80° to 135°C.
  • the treatment with TiCl 4 can be repeated.
  • the solid is then washed with hexane, or other hydrocarbon solvents, in order to eliminate all traces of nonreacted TiCl 4 .
  • Another method is based on the reaction between a MgCl 2 ⁇ nROH adduct (particularly in spheroidal particle form), where n is generally a number from 1 to 3 and ROH is ethanol, butanol, or isobutanol, and an excess of TiCl 4 containing the electron-donor compound in solution.
  • the reaction temperature generally ranges from 80 to 120°C.
  • the solid is then separated and caused to react one or more times with TiCl 4 , then washed with a hydrocarbon solvent in order to eliminate all traces of nonreacted TiCl 4 .
  • An alternative method consists of reacting the magnesium alcoholates and chloro-alcoholates (the latter prepared in particular according to the method described in U.S. patent no. 4,220,554), with an excess of TiCl 4 containing the electron-donor compound in solution, operating under the same reaction conditions described above.
  • the titanium compound in the solid catalyst component is present from 0.5 to 10% by weight, and the quantity of electron-donor compound which remains fixed on the solid component (internal donor), generally ranges from 5 to 20% in moles with respect to the magnesium dihalide.
  • the titanium compounds which can be used for the preparation of the solid catalyst component (a) are the titanium halides and the halo-alcoholates. Titanium tetrachloride is the preferred compound.
  • titanium trihalides particularly TiCl 3 HR, TiCl 3 ARA, and titanium haloalcoholates, such as TiCl 3 OR, where R is a phenyl radical.
  • the active form of the magnesium dihalides in the solid catalyst components is revealed by the fact that in the X-ray spectrum of the catalyst component the major intensity reflection shows a half-peak breadth at least 30% greater than the one of the major intensity reflection which appears in the unactivated Mg dihalide spectrum, or by the fact that the major intensity reflection, which appears in the spectrum of the unactivated magnesium dihalide (having a surface area smaller than 3 m 2 /g), is no longer present, but in its place there is a halo with the intensity maximum shifted respect to the position of the major intensity reflection of the unactivated magnesium dihalide.
  • the chloride is the preferred compound.
  • the X-ray spectrum of the catalyst component shows a halo instead of the reflection which in the spectrum of the unactivated magnesium chloride appears at a distance of 2.56 ⁇ .
  • Al-alkyl compounds used as co-catalysts are of the trialkyl aluminum type, such as Al-triethyl, Al-triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded by way of O or N atoms, or SO 2 , SO 3 and SO 4 groups.
  • Some examples of these compounds are: (C 2 H 5 ) 2 Al-O-Al(C 2 H 5 ) 2 , (C 2 H 5 ) 2 Al-N(C 6 H 5 )-Al(C 2 H 5 ) 2 , (C 2 H 5 ) 2 Al-SO 2 -Al(C 2 H 5 ) 2 , CH 3 [(CH 3 )Al-O] n -Al(CH 3 ) 2 , -[(CH 3 )Al-O] n -, where n is a number from 1 to 20.
  • the Al-alkyl compound is generally present in such quantities that the Al/Ti ratio ranges from 1 to 1000.
  • the electron-donor compounds which can be used as external donors (added together with the Al-alkyl compound) comprise the esters of aromatic acids (such as alkyl benzoates), heterocyclic compounds (such as 2,2,6,6-tetramethylpiperidine, and 2,6-diisopropylpiperidine) and particularly silicon compounds containing at least one Si-OR bond (where R is a hydrocarbon radical).
  • Some examples of silicon compounds are: (t-C 4 H 9 ) 2 Si(OCH 3 ) 2 , (C 6 H 11 ) 2 Si(OCH 3 ) 2 , and (C 6 H 5 ) 2 Si(OCH 3 ) 2 .
  • the 1,3-diethers of formula (I) can also be used advantageously as external donors. In the case where the internal donor is one of the 1,3-diethers of formula (I) the external donor can be omitted.
  • the polymerization is carried out in at least two stages, during which Fractions A and B of the present invention are prepared.
  • the fractions are formed in separate and in sequential stages. In each stage the operation takes place in the presence of the polymer obtained and the catalyst used in the preceding stage.
  • the order in which Fractions A and B are prepared is not important, however, it is preferred to prepare first Fraction A and then Fraction B.
  • the polymerization process can be carried out in liquid phase, in the presence or absence of inert solvent, or in gas phase, or using mixed liquid and gas phases.
  • the preferred process is the one which is carried out in gas phase.
  • the length and temperatures of polymerization during the polymerization stages are not critical; at any rate the preferred temperature range is from 20° to 100°C.
  • the regulation of the molecular weight is done by using known regulators, preferably hydrogen.
  • the polymerization process can be preceded by a prepolymerization process where the catalyst is caused to contact with small quantities of olefins.
  • the hot reaction mix is then transferred in an inert atmosphere to a 1500 ml vessel equipped with heating jacket, containing 150 ml of vaseline oil and 150 ml of silicon oil.
  • the mixture is maintained at 120°C while the contents are stirred by way of an Ultra Turrax T-45 N agitator of the Janke & Kunkel K.G. Ika Werke. The stirring continues for 3 minutes at 3000 rpm.
  • the mixture is then discharged into a 2 liter vessel containing 1000 ml of anhydrous n-heptane, kept under agitation and cooled in such a way that the temperature does not exceed 0°C.
  • the microspheres of MgCl 2 ⁇ 3C 2 H 5 OH thus obtained are recovered by filtration and dried under vacuum at room temperature.
  • the resulting adduct is then dealcoholated by gradually increasing the temperature from 50° to 100°C under nitrogen flow until the alcohol content goes down to 1.5 moles per mole of MgCl 2 .
  • the partially dealcoholated adduct has a surface area of 9.1 m 2 /g and an apparent density of 0.564 g/cm 3 .
  • the contents of the reactor are heated to 100°C for two hours, then the solids are allowed to settle, and the hot liquid is syphoned off.
  • the solid is washed six times using 200 ml of anhydrous hexane at 60°C, and finally three times at room temperature.
  • the solid after having been dried under vacuum, has the following characteristics:
  • the polymerization tests have been carried out in a 22 liter stainless steel autoclave equipped with magnetic helical agitator rotating at about 90 rpm.
  • the gas phase is analyzed in continuous by way of a process gas-chromatograph in order to determine the concentration of l-butene, propylene and hydrogen.
  • the l-butene, propylene, and hydrogen are fed using flow-meter regulators in order to maintain a constant concentration in the gas phase.
  • the reaction is carried out at constant temperature and pressure, unless otherwise specified.
  • the batch operation is conducted in two stages, both in gas phase: during the first stage one carries out the copolymerization of the propylene with the 1-butene to obtain fraction A, during the second stage one carries out the polymerization of the same comonomers to obtain fraction B.
  • the polymer is discharged from the bottom of the autoclave, stabilized with pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate] (0.2% by weight), and 2,6-di-tert-butyl-para-cresol (BHT) (0.2% by weight), and dried in an oven under nitrogen flow at 60°C.
  • pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate] (0.2% by weight
  • BHT 2,6-di-tert-butyl-para-cresol

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Medicinal Preparation (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (8)

  1. Une composition de polyoléfine semi-cristalline comprenant (en poids) :
    A) de 25 à 50 % d'un copolymère statistique propène/α-oléfines en C4-C10 (fraction A), contenant de 1 à 10 % d'α-oléfines en C4-C10 ;
    B) 50 à 75 % d'un copolymère statique propène/α-oléfines en C4-C10 (fraction B), contenant de 15 à 40 % d'α-oléfines en C4-C10, identique ou différent de celui qui est présent dans la fraction (A),
    dans laquelle le pourcentage en poids de fraction (B) (% B) exprimé par rapport au poids total de la composition et le pourcentage en poids d'α-oléfines en C4-C10 dans la fraction (B) (C4 B) satisfont la relation % B x C4 B ≥ 1200, la proportion de fraction soluble en xylène à 25°C est inférieure à 16 % en poids, le point de fusion est de 135 à 150°C et la température de thermosoudage est de 90 à 105°C.
  2. La composition selon la revendication 1, dans laquelle les α-oléfines en C4-C10 des fractions (A) et (B) sont identiques.
  3. La composition selon la revendication 1, dans laquelle l'α-oléfine en C4-C10 est choisie dans le groupe consistant en 1-butène, 1-pentène, 1-hexène, 1-octène et 4-méthyl-1-pentène.
  4. La composition selon la revendication 1 dans laquelle le pourcentage en α-oléfines en C4-C10 de la fraction (A) est de 3 à 8 % en poids.
  5. La composition selon la revendication 1, dans laquelle le pourcentage en α-oléfines en C4-C10 de la fraction (B) est de 20 à 30 % en poids.
  6. Un procédé de préparation d'une composition selon la revendication 1, dans lequel les monomères sont polymérisés en présence de catalyseurs stéréo-spécifiques supportés sur des dihalogénures de magnésium actifs sous forme active, en au moins deux étapes distinctes et successives. où on forme les fractions (A) et (B), chaque étape étant effectuée en présence du polymère formé et du catalyseur utilisé dans l'étape immédiatement précédente.
  7. Le procédé selon la revendication 6, dans lequel toutes les étapes de polymérisation sont effectuées en phase gazeuse.
  8. Le procédé selon la revendication 6, dans lequel la première étape est effectuée dans le monomère liquide et la seconde étape est effectuée en phase gazeuse.
EP93103846A 1992-03-10 1993-03-10 Compositions de copolymères statistiques de propène et comonomères d'alpha-olefines Expired - Lifetime EP0560326B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI920545A IT1254244B (it) 1992-03-10 1992-03-10 Composizioni di copolimeri random del propene contenenti una alfa- olefina come comonomero
ITMI920545 1992-03-10

Publications (2)

Publication Number Publication Date
EP0560326A1 EP0560326A1 (fr) 1993-09-15
EP0560326B1 true EP0560326B1 (fr) 1997-05-28

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EP (1) EP0560326B1 (fr)
JP (1) JP3452601B2 (fr)
KR (1) KR100253015B1 (fr)
CN (1) CN1082979C (fr)
AT (1) ATE153683T1 (fr)
AU (1) AU664598B2 (fr)
BR (1) BR9301113A (fr)
CA (1) CA2091299C (fr)
DE (1) DE69310961T2 (fr)
ES (1) ES2103990T3 (fr)
FI (1) FI112245B (fr)
IT (1) IT1254244B (fr)
MX (1) MX9301317A (fr)
NO (1) NO301771B1 (fr)
RU (1) RU2104289C1 (fr)
TW (1) TW281681B (fr)

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FI931040A (fi) 1993-09-11
NO301771B1 (no) 1997-12-08
TW281681B (fr) 1996-07-21
CN1076937A (zh) 1993-10-06
BR9301113A (pt) 1993-09-14
AU3513893A (en) 1993-09-16
DE69310961D1 (de) 1997-07-03
EP0560326A1 (fr) 1993-09-15
ITMI920545A0 (it) 1992-03-10
KR100253015B1 (ko) 2000-04-15
NO930863L (no) 1993-09-13
JPH0693146A (ja) 1994-04-05
DE69310961T2 (de) 1997-11-27
NO930863D0 (no) 1993-03-09
JP3452601B2 (ja) 2003-09-29
IT1254244B (it) 1995-09-14
FI112245B (fi) 2003-11-14
ATE153683T1 (de) 1997-06-15
CA2091299A1 (fr) 1993-09-11
AU664598B2 (en) 1995-11-23
KR930019750A (ko) 1993-10-18
ITMI920545A1 (it) 1993-09-10
MX9301317A (es) 1993-09-01
ES2103990T3 (es) 1997-10-01
RU2104289C1 (ru) 1998-02-10
CN1082979C (zh) 2002-04-17
FI931040A0 (fi) 1993-03-09
CA2091299C (fr) 2001-06-12

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